Composition of matter, method of making same, and improved lubricating oil



4Patented Feit.y 22, 1944 I I The polyb'asic a'cid plated "as lreactants forV pf c1ass offcomp grit abou 1 b'y,-heeltine @ated-temperatura etime'sat'temp'era- 'ftslfo'rmedare also ctiohappears in is weil 'kn tha maleicj h'ydr'idgzand other alpha-betaetlflylenl acids bij lanhycii'dos. 50,.

Will condense Withconjugated, unsatuiiatedlatty I pending to.' suhfjacids. Actually they are i acids in accordance `with Thiele'stheoryot l1 -4' ecqgi'zedqfag,being functionally equivalent in addition. 'I he fatty' acid in this case; of course, Condensationsfol the kinds heiein contemplated. must contain at; least two carbon-tocalbcn "Suitable"' oi'conjuaf unsaturated non* double bondsand these must beconjugated, .This 55'. hydoxylated fatty 'acids for use in condensation the c iaimsjtb'falpha-beta. unsaturated acids "is tendedjto include the anhydrides corrieaforemntmnedreactions@ with-z4 the above-mentioned` alphagbetaethylenic acidsare thosefcontainingfrom mito-24 carbon atoms .in their carbon: chains, and in-. clude undecylenic'acid', oleicacid, elaidic acid..

besemployed in this condensation inplace of the fatty acid itself. In the present specication and in the claims.- the term non-conjugated..

- unsaturated, non-.hydroxylated fattyj acids is intended toinclude the. estershof. such: acids: with.

mono-, di, or polyhydric alcohols. For the. productionoi the present compositions using as one of. the amic-lei-products: and'y for' the.; purposes; of

the present: inventiontthe term'.alkyl as applied" in. describing-Suitable'. amines isa-intended to in-l clude oletinic residues whiclrcan be considered i as being derived'` from Aan alkyl; residue by dehydrogenation;V Suitableolenic amines; include'y oleyl` amine undecenylr -amine, hexadecenyl amine eicose'nyl. amine, dioctadecenyi' amine, methylhexadecenylV amine, and the like.

For convenience ink describing the reactions involved. inl preparings. the.. present` products, the

diene synthssizadducts.' andv the Clocker adducts.

will h e A referred@ ta simply as unsaturated 'fatty acid adlviucts, andi this. term; is.. also-.intended to refer to .adductslderived :from the. esters-vY of thel unsaturatedffattylacidsl. Inthe examples. itl will reactant the abovedescribed.condensationcom v A of! the diene; synthesis type'or the Clocker poundsof Clocker, I usually prefer to employ a condensationproduct'derived from aglyceride containing, in esterifiedzforma large proportion of non-conjugated; unsaturated. non-hydroxyl gated .fatty acid.. Examplesf of 'suchglycerides are olive oil, com oil', cottonseedl oil', linseed'oil, 'fBOya-bean oil.. rapeseed-l oi1,"perilla oil, cranberry seed oil,'. menhaden oil. cod oil, whale oil, heat ..bodiedglinseed' oil, etc.

,@When glycerides or other esters of the nonconjugated, unsaturated, non-hydroxylated fatty acids areiemployed in the condensation reaction,

the final product is not -necessarily a polybasic acid or anhydride, since a monocarboxy, alpha` beta ethylenic-.acid such as. crotonic acid, may have been employed in thecondensation. How-- ever, such monobasic. acid condensation `products are contemplated as reactants inv preparing my newwcompositions; and they are intended to be included. when referenceis made to aV polybasic carboxyacid l or` anhydride. reactant.

.Actually they are. the partial esters` of dibasic acids and .under certain conditions may function as polyfbasic acids by interchange of the alcohol residue with a hydroxyl-containing reactant.

As previously stated, my new compositions may bev preparedzby condensing .a diene synthesis adduct or a Cloclrer adduct and a high molecu- 1arweight amine. The amines used .are primary or secondary and must contain at least one alkyl residue of from 8 to 32 carbon latoms in size, but in addition may -contain y other hydrocarbon groups or residues such as aromatic rings, alicyclic rings, or heterocyclic lrings in which the aminonitrogen is a part of the ring. The amino Vgroup may be attached either to the alkyl residue or to the non-alkyl portion of the molecule, but

of course must'be capable of forming an amide orv imide by reaction with the Clocker adduct. Tl'iese amines mayl be either straight or branch chained and may be either primary or secondary.

Examples of suitable amine reactants include 'the following: n-octyl amine, 2-ethy1 hexylamine, lauryl amine, hexadecyi amine, octadecyl amine', docosylamine, para-iso-octyl aniline. di-

be clearfwhetherthe. adductv reactant. employed:

type.. A: mixturef. of`. the tworI-maybe employed if class-cf compounds;it1ismsual1y-mostconvenient Y to preparethe desired adduct'ofithel-unsaturated fattyacid' and'ian--alphafbetafethylenicfacim Vafter which-the desired" high: molecularfweightaamine. is` added andre'acted.byheatinmandtirring; It. is not necessary that. alli-of; thefcarboxylson potenual anhydride carboxylase the: adduct be.

conclensed`v with' high 'molecular-.weight amines,

and, as will loe-'discussed hereinaftensome: carboxyls. will o ftenbeflet; The following examples illustrate the preparation-'cumulent theA present4 Products..V

benzol, anda-smalrcrystali otfiodine;

Example?.

75 irlTungl oil vlas substituted for the tung oil acids ExamplelfThe productiinthisicase was quite soluble in kerosene. and lubricatingl oil and was superior in pour point depressing properties. to the product' of Example 1f;

Example 42 g. of' crotonic acidi-were substituted: for-the '5 0 g. of mal'eic anhydride infExamplefZ, andonly 92 g. of dodecylamine were employed: in the amidication step.

Example 4'y A Clocker adductiv was prepared by heating and stirring under an airl condensera mixture -of 3D0 g. of lnseed oil and200 g. of-'citraconic anhydride.

The temperaturev of this mixturewas slowly raised to 230` C. and held at this point for 2% hrs.

50 g. of the above addvuctv was heated and stirred in an open vessel with 50 g. of.' hexadecylamine. The temperature was raised 1:0240v C. and held for 45 minutes. 'I'he'inal` product was a viscous oil.

Example. 5l

Maleic anhydride was substituted for thetcitraconic anhydride of Example 4.

' .mary amines.

` an ammonium;A amino, or metal ion. havingdetergent. and' sludge'dispersing properln'o'leriate-waasubstituted for the 1in- ...E-@mele 7 00. g;.otsoybean'oil-and.100 g. of maleic anhyto.240" C. andtheld at this .point for 3 hrs. 50 g. of the' above adduct and 35 g. of octa- -decenylamine.were heated and ,stirred in an open beaker for'y 1 hr.-,atfa temperature of 250" C. The

` product was. aviscous oil havingy good pour point :depressant action von a Gulf Coast lubricating oil.

Example 8 Example 9' .soogf-f tu yclearerreducver. Example 4 was reacted'with 4104:2 g'. of 'dioctadecyl amine by heatingandstimpggrqraiirsliafter raising the tem- 'Irr-some"ofgthefexamples given above. less aminehas'beenused vinthe reaction than correspends toallfo! thefcarboxyls or potential car- Vjboxyls.present'lin.theadduct.. AIn such cases the Aproduct may 'contain free carboxyl groups.

Where .5a primaryamine is reacted with an adl ductcontaining tw'o carboxylic acid groups which are-'attached'.td closelyadjacent Carbon atoms,

the. product..l appears tol contain appreciable amountsof'anfy imide, 'as well ls some'amide.

v anhydride, ci'traconic anhydride fumarie acid Yand,other.polycarboxylic; alpha-beta unsaturated acids in which two carboxyl groups -are separated by only two carbon atoms appear tobe most ca- 'pableofyielding imides when reacted with pri- Aniimide-maybe: looked upon as a special kind efrfamidefionelfinfwhich two, instead of one, or

vthe'-amine..hydiiogeris'have been removed by an lacylationgv reaction. Consequently, in order to simplify nomenclature, the term amlde" will be employed: herein and in the claims to designate the products obtainedby acylation reaction between the diene adduct or ACloclrer adduct and tnejamm'es-of the llundidescribed, whether Such ac ylation lresultsfin' the removal of one or two amino hydrogen4 atoms. In general, reactions involvi'ng'primaryamines will'contain at least some of 'each type: offa'cylation product.

'unreai-,tedY carboxylic acid or anhydride groups remaining virl-'the product may be left as suchy` o'r- :nay-- be -neutralized with ammonia, amines, or 'inorganicfbases` in which case the acidic hydrogen-of the' carboxyl is replaced with Products 'tiesima'y befprepared, for` example, by treating Athe product of Example 9 with calcium hydroxide,

to neutralize free carboxy acid groups, heating to'complete the reaction and drive oifl water, dissolving in ligroin, filtering to remove unused calcium hydroxide, and evaporating ligroin from theltrate.

Similar products may be prepared from the compounds of the other examples where free anhydride or carboxyl groups are present.

If desired, residual carboxy acid groups may be esteried with low molecular weight alcohols to yield products with improved oil solubility. l

Residual carboxy acid groups may be reacted with phenols, for 'example, phenol; catechol..

reagents may be left as such or may be replaced by any equivalent. Such acidicv products may be treated with a suitable alkaline materialsuch as caustic soda, caustic potash, ammonium hydroxide,A calcium hydroxide, magnesium hy'- droxide, etc., to form the corresponding metallic salts, or with'arnines such as amylamine, cyclo.- hexylamine, triethanolamineppara `amino'` phenol, etc., to form theamine salts. The acidic hydrogen may be 'replaced by 'a lower alcohol residue derived from alcohols such as ethanol, butanol, hexanol, cyclohexanol, phenol, cate'- chol, etc., to form an ester. Amino alcohols such as the ethanolami'nes.- glyceryl amines, etc.. may be employed to replacean acidic hydrogen either by esteritlca'tionorsalt'formation. v

The present class of chemical productsv ap-- pears to haveits greatest usefulness-in the 'field of lubricating oil additives and rust preventers, and are particularly eiective pour point depressants for waxy or paraiiinic lubricating oils. They are also very effective in modifyingA the crystalline form of wax crystals and may-be employed for this purpose to Aobtain' more' easl1y filterable wax cakes during dewaxing operations. When used as pour point1depressants inrlubricating oils ,the present materials are generally eiective in proportions varying between'0.0l% vand 2% based on the weight of oil.

Certain of the present Acompounds also have detergent and sludge dispersing'propertiesand when used in lubricating oil are effectivejn pre-l venting sludge and varnish deposition inl enproperty of inhibiting or greatly lessening. the

corrosion of ferrous metals when applied" to such metals directly or in the form* of solutions in oils or greases.

Others of these reagents have the property-'0f increasing the oiliness of load-bearing capacityof oils; and still others have antioxidant properties.

It will be obvious to most chemistsv that various derivatives of the present products may be prepared which will have similar properties. For example, many of the present products contain carbon-to-carbon double bonds, either in the fatty acid or amine residue chain. and may be readily sulfurized by heating with sulfur. Such sulfurized derivatives, in some instances, have valuable properties over and above the original unsulfurized product. For example. they usually are better antioxidants and have greater film strength as lubricants.

Other obvious derivatives include those derivable by oxidation, as by blowing with airor oxygen at elevated temperatures. and polymerized products derivable by reacting carboxyl or anhydride containing compositions with polyhydric alcohols or polyamines.

It is to be understood that the new compounds or compositions previously referred to may und various uses as well as lubricating. oil additives. 

